U.S. patent number 5,405,412 [Application Number 08/226,915] was granted by the patent office on 1995-04-11 for bleaching compounds comprising n-acyl caprolactam and alkanoyloxybenzene sulfonate bleach activators.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Michael E. Burns, Jerome H. Collins, Alan D. Willey.
United States Patent |
5,405,412 |
Willey , et al. |
April 11, 1995 |
Bleaching compounds comprising N-acyl caprolactam and
alkanoyloxybenzene sulfonate bleach activators
Abstract
Laundry detergents and automatic dishwashing compositions with
activated bleaching systems which are effective under mixed soil
conditions, especially mixtures of hydrophobic and hydrophilic
soils and stains are presented. The preferred bleach activators are
N-acyl caprolactams and nonanoyloxybenzene sulfonate. A
particularly preferred embodiment comprises a 1:2.2:7.7 molar ratio
of N-acyl caprolactam to alanoyloxybenzenesulfonate to peroxygen
bleaching compound. This mixed caprolactam,
alkanoyloxybenzenesulfonate bleaching composition delivers stronger
than expected performance on both hydrophobic and hydrophilic
stains and on dingy clean up.
Inventors: |
Willey; Alan D. (Cincinnati,
OH), Burns; Michael E. (West Chester, OH), Collins;
Jerome H. (Cincinnati, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
22850967 |
Appl.
No.: |
08/226,915 |
Filed: |
April 13, 1915 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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64627 |
May 20, 1993 |
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Current U.S.
Class: |
8/111; 134/2;
252/186.39; 252/519.21; 252/519.3; 510/220; 510/226; 510/228;
510/294; 510/300; 510/306; 510/312; 510/376; 510/495; 510/500;
8/137 |
Current CPC
Class: |
C11D
3/3907 (20130101) |
Current International
Class: |
C11D
3/39 (20060101); C11D 003/28 (); C11D 003/395 ();
C11D 003/34 (); C11D 003/02 () |
Field of
Search: |
;252/99,102,524,542,186.39 ;8/111,137 ;134/2 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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A068547 |
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Jan 1983 |
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EP |
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A57700 |
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Mar 1988 |
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EP |
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1596313 |
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Aug 1981 |
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GB |
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2189520 |
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Oct 1987 |
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GB |
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Primary Examiner: Albrecht; Dennis
Attorney, Agent or Firm: Jones; Michael D. Yetter; Jerry J.
Rasser; Jacobus C.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No.
08/064,627, filed May 20, 1993, now abandoned.
Claims
What is claimed is:
1. A bleaching composition comprising:
i) a peroxygen bleaching compound;
ii) a hydrophilic N-acyl caprolactam bleach activator wherein the
acyl moiety of said N-acyl caprolactam is of the formula R.sup.1
--C(O)-- wherein R.sup.1 is H or an alkyl or aryl group containing
from about 1 to about 6 carbon atoms; and
iii) an alkanoyloxybenzenesulfonate bleach activator, wherein said
alkanoyl moiety contains from about 8 to about 12 carbon atoms;
such that the molar ratio of N-acyl
caprolactam:alkanoyloxybenzenesulfonate:peroxygen bleaching
compound is approximately 1:2.2:7.7.
2. A bleaching composition according to claim 1 wherein said N-acyl
caprolactam is selected from the group consisting of benzoyl
caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl
caprolactam, butanoyl caprolactam, pentanoyl caprolactam, hexanoyl
caprolactam, and mixtures thereof; said alkanoyloxybenzenesulfonate
is selected from the group consisting of
nonanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate,
octanoyloxybenzenesulfonate, dodecanoyloxybenzenesulfonate,
3,5,5-trimethylhexanoyloxybenzenesulfonate,
2-ethylhexanoyloxybenzenesulfonate, and mixture thereof; and said
peroxygen bleaching compound is selected from the group consisting
of sodium perborate monohydrate, sodium perborate tetrahydrate,
sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium
percarbonate, sodium peroxide, and mixtures thereof.
3. An automatic dishwashing composition comprising a bleaching
composition according to claim 1.
4. A laundry detergent composition comprising a bleaching
composition according to claim 1.
5. A laundry detergent composition according to claim 4 wherein
said bleaching composition comprises:
i) about 0.85% benzoyl caprolactam;
ii) about 3% nonanoyloxybenzenesulfonate; and
iii) about 3% perborate bleaching compound.
6. A method for cleaning fabrics, dishes, or hard surfaces, said
method comprising contacting said fabrics, dishes, or hard surfaces
with a bleaching composition according to claim 1.
7. A method according to claim 6 wherein said N-acyl caprolactam is
selected from the group consisting of benzoyl caprolactram, formyl
caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl
caprolactam, pentanoyl caprolactam, hexanoyl caprolactam, and
mixtures thereof; said alkanoyloxybenzenesulfonate is selected from
the group consisting of nonanoyloxybenzenefulfonate,
decanoyloxybenzenesulfonate, octanoyloxybenzenefulfonate,
dodecanoyloxybenzenesulfonate,
3,5,5-trimethylhexanoyloxybenzenesulfonate,
2-ethylhexanoyloxybenzenesulfonate, and mixture thereof; and said
peroxygen bleaching compound is selected from the group consisting
of sodium perborate monohydrate, sodium perborate tetrahydrate,
sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium
percarbonate, sodium peroxide, and mixtures thereof.
8. A method according to claim 7 wherein said N-acyl caprolactam is
benzoyl caprolactam, said alkanoyloxybenzenesulfonate is
nonanoyloxybenzenesulfonate, and said peroxygen bleaching compound
is selected from the group consisting of sodium perborate
monohydrate, sodium perborate tetrahydrate, sodium percarbonate,
and mixtures thereof.
Description
FIELD OF THE INVENTION
The present invention relates to laundry detergents and automatic
dishwashing compositions with activated bleaching systems which are
effective under mixed soil conditions, especially mixtures of
hydrophobic and hydrophilic soils and stains.
BACKGROUND OF THE INVENTION
It has long been known that peroxygen bleaches are effective for
stain and/or soil removal from fabrics, but that such bleaches are
temperature dependent. At a laundry liquor temperature of
60.degree. C., peroxygen bleaches are only partially effective. As
the laundry liquor temperature is lowered below 60.degree. C.,
peroxygen bleaches become relatively ineffective. As a consequence,
there has been a substantial amount of industrial research to
develop bleaching systems which contain an activator that renders
peroxygen bleaches effective at laundry liquor temperatures below
60.degree. C.
Numerous substances have been disclosed in the art as effective
bleach activators. One widely-used bleach activator is tetraacetyl
ethylene diamine (TAED). TAED provides effective hydrophilic
cleaning especially on beverage stains, but has limited performance
on dingy stains and body soils. Another type of activator, such as
nonanoyloxy-benzenesulfonate (NOBS) and other activators which
generally comprise long chain alkyl moieties, is hydrophobic in
nature and provides excellent performance on dingy stains.
It would seem that a combination of bleach activators, such as TAED
and NOBS, would provide an effective detergent composition which
would perform well on both hydrophilic and hydrophobic soils and
stains. However, many of the hydrophilic activators developed thus
far, including TAED, have been found to have limited efficacy,
especially at laundry liquor temperatures below 60.degree. C.
Another consideration in the development of consumer products
effective on both types of soils is the additional costs associated
with the inclusion of two or more bleach activators. Accordingly,
it is of substantial interest to the manufacturers of bleaching
systems to find a less expensive type of hydrophilic bleaching
activator.
By the present invention, it has now been discovered that the class
of bleach activators derived from hydrophilic N-acyl caprolactams
performs very well when combined with the cleaning performance of
hydrophobic alkanoyloxybenzenesulfonate and has the added benefit
of being relatively inexpensive to manufacture. Accordingly, the
present invention solves the long-standing need for an inexpensive
bleaching system which performs efficiently and effectively at low
temperatures and under mixed soil load conditions, especially
mixtures of hydrophobic and hydrophilic soils.
BACKGROUND ART
U.S. Pat. No. 4,545,784, Sanderson, issued Oct. 8, 1985, discloses
the adsorption of activators onto sodium perborate monohydrate.
U.S. Pat. No. 4,412,934, Chung et al, issued Nov. 1, 1983,
discloses alkanoyloxybenzenesulfonate activators, including the
preferred nonanoyloxybenzenesulfonate activator used herein.
SUMMARY OF THE INVENTION
The present invention relates to bleaching systems and methods
which employ them for cleaning fabrics under mixed soil load
conditions. Said bleaching system comprises:
a) at least about 0.1%, preferably from about 1% to about 75%, by
weight, of a peroxygen bleaching compound capable of yielding
hydrogen peroxide in an aqueous solution;
b) at least about 0.1%, preferably from about 0.1% to about 50%, by
weight, of one or more hydrophilic N-acyl caprolactam bleach
activators; and
c) at least about 0.1%, preferably from about 0.1% to about 50%, by
weight, of a hydrophobic alkanoyloxybenzenesulfonate bleach
activator.
The preferred alkanoyl moieties of said alkanoyloxybenzenesulfonate
bleach activators contain from about 8 to about 12 carbon atoms,
preferably from about 8 to about 11 carbons. Highly preferred
moieties are members selected from the group consisting of
octanoyl, nonanoyl, decanoyl, dodecanoyl, 3,5,5-trimethylhexanoyl,
2-ethylhexanoyl, and mixtures thereof.
The acyl moieties of said N-acyl caprolactam bleach activators have
the formula R.sup.1 --CO-- wherein R.sup.1 is H or an alkyl or
aryl, group containing from about 1 to about 6 carbon atoms. In
preferred embodiments, R.sup.1 is a member selected from the group
consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, and
phenyl substituents.
The peroxygen bleaching compound can be any peroxide source, and is
preferably a member selected from the group consisting of sodium
perborate monohydrate, sodium perborate tetrahydrate, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium
percarbonate, sodium peroxide and mixtures thereof. Highly
preferred peroxygen bleaching compounds are selected from the group
consisting of sodium perborate monohydrate, sodium perborate
tetrahydrate, sodium percarbonate and mixtures thereof. The most
highly preferred peroxygen bleaching compound is sodium
percarbonate.
The invention also encompasses detergent compositions in granular,
paste, liquid, or bar form which comprise the aforesaid bleaching
system together with detersive ingredients which are present in the
composition at the levels indicated hereinafter.
The bleaching method herein is preferably conducted with agitation
of the fabrics with an aqueous liquor containing the aforesaid
compositions at levels from about 50 ppm to about 27,500 ppm, and
is especially adapted for conditions in which the fabrics are
soiled with both hydrophobic and hydrophilic soils. The method can
be carded out at any desired washing temperature, even at
temperatures below about 60.degree. C., and is readily conducted at
temperatures in the range of from about 5.degree. C. to about
45.degree. C. The method can be conducted conveniently using a
composition which is in bar form, but can also be conducted using
granules, flakes, powders, pastes, and the like.
The aqueous laundry liquor typically comprises at least about 300
ppm of conventional detergent ingredients, as well as at least
about 25 ppm of the bleaching compound and at least about 25 ppm of
the mixture of bleach activators. Preferably, the liquor comprises
from about 900 ppm to about 20,000 ppm of conventional detergent
ingredients, from about 100 ppm to about 25,000 ppm of the
bleaching compound and from about 100 ppm to about 2,500 ppm of the
bleach activators. The conventional detergent ingredients and
bleaching system will typically be combined into a detergent
composition such as a granular laundry detergent or laundry
detergent bar.
The conventional detergent ingredients employed in said method and
in the compositions herein comprise from about 1% to about 99.8%,
preferably from about 5% to about 80%, of a detersive surfactant.
Optionally, the detergent ingredients comprise from about 5% to
about 80% of a detergent builder. Other optional detersive adjuncts
can also be included in such compositions at conventional usage
levels.
All percentages, ratios, and proportions herein are by weight,
unless otherwise specified. All documents cited are incorporated
herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The bleaching system employed in the present invention provides
effective and efficient surface bleaching of fabrics which thereby
removes stains and/or soils from the fabrics. The bleaching system
is particularly efficient at cleaning a mixture of soil loads,
especially mixtures of hydrophobic and hydrophilic soils.
Hydrophobic soils are generally associated with lipid and
protein-based soils and stains, such as body soils, blood, etc.,
but are also effective on so-called "dingy soils". Dingy soils are
those that build up on textiles after numerous cycles of usage and
washing, and result in a gray or yellow tint on white fabrics.
Hydrophilic soils include food and beverage stains.
The bleaching mechanism and, in particular, the surface bleaching
mechanism are not completely understood. However, it is generally
believed that the N-acyl bleach activator undergoes nucleophilic
attack by a perhydroxide anion, which is generated from the
hydrogen peroxide evolved by the peroxygen bleaching compound, to
form a peroxycarboxylic acid. This reaction is commonly referred to
as perhydrolysis. It is also believed, that the N-acyl and
alkanoyloxybenzenesulfonate bleach activators within this invention
can render peroxygen bleaches more efficient even at laundry liquor
temperatures wherein bleach activators are not necessary to
activate the bleach, i.e., above about 60.degree. C. Therefore,
with bleach systems of the invention, less peroxygen bleach is
required to achieve the same level of surface bleaching performance
as is obtained with the peroxygen bleach alone.
The components of the bleaching system herein comprise the bleach
activator and the peroxide source, as described hereinafter.
Bleach Activators
The bleach activators of type b) employed in the present invention
are hydrophilic N-acyl caprolactams of the formula: ##STR1##
wherein R.sup.1 is H or an alkyl, aryl, alkaryl, or alkoxyaryl
group containing from about 1 to about 6 carbon atoms. Caprolactam
activators wherein the R.sup.1 moiety contains from about 1 to
about 6 carbon atoms provide hydrophilic bleaching which affords
beverage and food stain removal.
Benzoyl caprolactam, i.e., wherein R.sup.1 is a phenyl substituent,
has now been found to be unique among the bleach activator
compounds, inasmuch as it appears to exhibit both hydrophobic and
hydrophilic bleaching activity. This hydrophobic/hydrophilic
bleaching capability makes benzoyl caprolactam the activator of
choice for the formulator who is seeking broad spectrum bleaching
activity, and wishes to use a single caprolactam activator for
hydrophilic cleaning and for additional hydrophobic performance in
combination with the alkanoyloxybenzenesulfonate activator.
Highly preferred hydrophilic N-acyl caprolactams are selected from
the group consisting of formyl caprolactam, acetyl caprolactam,
propanoyl caprolactam, butanoyl caprolactam, pentanoyl caprolactam,
hexanoyl caprolactam, and benzoyl caprolactam.
Methods of making N-acyl caprolactams are well known in the art.
Example I, included below, illustrates a preferred laboratory
synthesis. Contrary to the teachings of U.S. Pat. No. 4,545,784,
cited above, the bleach activator is preferably not absorbed onto
the peroxygen bleaching compound. To do so in the presence of other
organic detersive ingredients could cause safety problems.
The bleach activators of type c) employed in the present invention
are alkanoyloxybenzenesulfonates of the formula: ##STR2## wherein
R.sup.1 --C(O)-- contains from about 8 to about 12, preferably from
about 8 to about 11, carbon atoms and M is a suitable cation, such
as an alkali metal, ammonium, or substituted ammonium cation, with
sodium and potassium being most preferred.
Highly preferred hydrophobic alkanoyloxybenzenesulfonates are
selected from the group consisting of nonanoyloxybenzenesulfonate,
3,5,5-trimethylhexanoyloxybenzenesulfonate,
2-ethylhexanoyloxybenzenesulfonate, octanoyloxybenzenesulfonate,
decanoyloxybenzenesulfonate, dodecanoyloxybenzenesulfonate, and
mixtures thereof.
The bleaching system comprises at least about 0.1%, preferably from
about 0.1% to about 30%, more preferably from about 1% to about
30%, most preferably from about 3% to about 25%, by weight, of type
b) and type c) bleach activators.
When the activators are used, optimum surface bleaching performance
is obtained with washing solutions wherein the pH of such solution
is between about 8.5 and 10.5, preferably between 9.5 and 10.5, in
order to facilitate the perhydrolysis reaction. Such pH can be
obtained with substances commonly known as buffering agents, which
are optional components of the bleaching systems herein.
The Peroxygen Bleaching Compound
The peroxygen bleaching compounds useful herein are those capable
of yielding hydrogen peroxide in an aqueous liquor. These compounds
are well known in the art and include hydrogen peroxide and the
alkali metal peroxides, organic peroxide bleaching compounds such
as urea peroxide, and inorganic persalt bleaching compounds, such
as the alkali metal perborates, percarbonates, perphosphates, and
the like. Mixtures of two or more such bleaching compounds can also
be used, if desired.
Preferred peroxygen bleaching compounds include sodium perborate,
commercially available in the form of mono-, tri-, and
tetra-hydrate, sodium pyrophosphate peroxyhydrate, urea
peroxy-hydrate, sodium peroxide, and sodium percarbonate.
Particularly preferred are sodium perborate tetrahydrate, sodium
perborate monohydrate and sodium percarbonate. Sodium percarbonate
is especially preferred because it is very stable during storage
and yet still dissolves very quickly in the bleaching liquor. It is
believed that such rapid dissolution results in the formation of
higher levels of percarboxylic acid and, thus, enhanced surface
bleaching performance.
Highly preferred percarbonate can be in uncoated or coated form.
The average particle size of uncoated percarbonate ranges from
about 400 to about 1200 microns, most preferably from about 400 to
about 600 microns. If coated percarbonate is used, the preferred
coating materials include mixtures of carbonate and sulphate,
silicate, borosilicate, or fatty carboxylic acids.
The bleaching system comprises at least about 0.1%, preferably from
about 1% to about 75%, more preferably from about 3% to about 40%,
most preferably from about 3% to about 25%, by weight, of a
peroxygen bleaching compound capable of yielding hydrogen peroxide
in an aqueous solution.
The weight ratio of bleach activator to peroxygen bleaching
compound in the bleaching system typically ranges from about 2:1 to
1:5. In preferred embodiments, the ratio ranges from about 1:1 to
about 1:3.
The bleach activator/bleaching compound systems herein are useful
per se as bleaches. However, such bleaching systems are especially
useful in compositions which can comprise various detersive
adjuncts such as surfactants, builders, enzymes, and the like as
disclosed hereinafter.
Detersive Surfactant
The amount of detersive surfactant included in the fully-formulated
detergent compositions afforded by the present invention can vary
from about 1% to about 99.8%, by weight of the detergent
ingredients, depending upon the particular surfactants used and the
effects desired. Preferably, the detersive surfactants comprise
from about 5% to about 80%, by weight of the detergent
ingredients.
The detersive surfactant can be nonionic, anionic, ampholytic,
zwitterionic, or cationic. Mixtures of these surfactants can also
be used. Preferred detergent compositions comprise anionic
detersive surfactants or mixtures of anionic surfactants with other
surfactants, especially nonionic surfactants.
Nonlimiting examples of surfactants useful herein include the
conventional C.sub.11 -C.sub.18 alkyl benzene sulfonates and
primary, secondary, and random alkyl sulfates, the C.sub.10
-C.sub.18 alkyl alkoxy sulfates, the C.sub.10 -C.sub.18 alkyl
polyglycosides and their corresponding sulfated polyglycosides,
C.sub.12 -C.sub.18 alpha-sulfonated fatty acid esters, C.sub.12
-C.sub.18 alkyl and alkyl phenol alkoxylates (especially
ethoxylates and mixed ethoxy/propoxy), C.sub.12 -C.sub.18 betaines
and sulfobetaines ("sultaines"), C.sub.10 -C.sub.18 amine oxides,
and the like. Other conventional useful surfactants are listed in
standard texts.
One particular class of adjunct nonionic surfactants especially
useful herein comprises the polyhydroxy fatty acid amides of the
formula: ##STR3## wherein: R.sup.1 is H, C.sub.1 -C.sub.8
hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof,
preferably C.sub.1 -C.sub.4 alkyl, more preferably C.sub.1 or
C.sub.2 alkyl, most preferably C.sub.1 alkyl (i.e. methyl); and
R.sup.2 is a C.sub.5 -C.sub.32 hydrocarbyl moiety, preferably
straight chain C.sub.7 -C.sub.19 alkyl or alkenyl, more preferably
straight chain C.sub.9 -C.sub.17 alkyl or alkenyl, most preferably
straight chain C.sub.11 -C.sub.19 alkyl or alkenyl, or mixture
thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear
hydrocarbyl chain with at least 2 (in the case of glyceraldehyde)
or at least 3 hydroxyls (in the case of other reducing sugars)
directly connected to the chain, or an alkoxylated derivative
(preferably ethoxylated or propoxylated) thereof. Z preferably will
be derived from a reducing sugar in a reductive amination reaction;
more preferably Z is a glycityl moiety. Suitable reducing sugars
include glucose, fructose, maltose, lactose, galactose, mannose,
and xylose, as well as glyceraldehyde. As raw materials, high
dextrose corn syrup, high fructose corn syrup, and high maltose
corn syrup can be utilized as well as the individual sugars listed
above. These corn syrups may yield a mix of sugar components for Z.
It should be understood that it is by no means intended to exclude
other suitable raw materials. Z preferably will be selected from
the group consisting of --CH.sub.2 --(CHOH).sub.n --CH.sub.2 OH,
--CH(CH.sub.2 OH)--(CHOH).sub.n-1 --CH.sub.2 OH, --CH.sub.2
--(CHOH).sub.2 (CHOR')(CHOH)--CH.sub.2 OH, where n is an integer
from 1 to 5, inclusive, and R' is H or a cyclic mono- or
poly-saccharide, and alkoxylated derivatives thereof. Most
preferred are glycityls wherein n is 4, particularly --CH.sub.2
--(CHOH).sub.4 --CH.sub.2 OH.
In Formula (I), R.sup.1 can be, for example, N-methyl, N-ethyl,
N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or
N-2-hydroxy propyl. For highest sudsing, R.sup.1 is preferably
methyl or hydroxyalkyl. If lower sudsing is desired, R.sup.1 is
preferably C.sub.2 -C.sub.8 alkyl, especially nopropyl, iso-propyl,
n-butyl, iso-butyl, pentyl, hexyl and 2-ethyl hexyl.
R.sup.2 --CO--N< can be, for example, cocamide, stearamide,
oleamide, lauramide, myristamide, capricamide, palmitamide,
tallowamide, etc.
Detergent Builders
Optional detergent ingredients employed in the present invention
contain inorganic and/or organic detergent builders to assist in
mineral hardness control. If used, these builders comprise from
about 5% to about 80% by weight of the detergent compositions.
Inorganic detergent builders include, but are not limited to, the
alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy
polymeric metaphosphates), phosphonates, phytic acid, silicates,
carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates. However, non-phosphate builders
are required in some locales.
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiO.sub.2 :Na.sub.2 O ratio in the
range 1.6:1 to 3.2:1 and layered silicates, such as the layered
sodium silicates described in U.S. Pat. No. 4,664,839, issued May
12, 1987 to H. P. Rieck, available from Hoechst under the trademark
"SKS"; SKS-6 is an especially preferred layered silicate
builder.
Carbonate builders, especially a finely ground calcium carbonate
with surface area greater than 10 m.sup.2 /g, are preferred
builders that can be used in granular compositions. The density of
such alkali metal carbonate built detergents can be in the range of
450-850 g/l with the moisture content preferably below 4%. Examples
of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001
published on Nov. 15, 1973.
Aluminosilicate builders are especially useful in the present
invention. Preferred aluminosilicates are zeolite builders which
have the formula:
wherein z and y are integers of at least 6, the molar ratio of z to
y is in the range from 1.0 to about 0.5, and x is an integer from
about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially
available. These aluminosilicates can be crystalline or amorphous
in structure and can be naturally-occurring aluminosilicates or
synthetically derived. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Pat. No. 3,985,669,
Krummel, et al, issued Oct. 12, 1976. Preferred synthetic
crystalline aluminosilicate ion exchange materials useful herein
are available under the designations Zeolite A, Zeolite P (B), and
Zeolite X. Preferably, the aluminosilicate has a particle size of
about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present
invention include, but are not restricted to, a wide variety of
polycarboxylate compounds, such as ether polycarboxylates,
including oxydisuccinate, as disclosed in Berg, U.S. Pat. No.
3,128,287, issued Apr. 7, 1964, and Lamberti et al, U.S. Pat. No.
3,635,830, issued Jan. 18, 1972. See also "TMS/TDS" builders of
U.S. Pat. No. 4,663,071, issued to Bush et al, on May 5, 1987.
Other useful detergent builders include the ether
hydroxypolycarboxylates, copolymers of maleic anhydride with
ethylene or vinyl methyl ether, 1,3,5-trihydroxy
benzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid,
the various alkali metal, ammonium and substituted ammonium salts
of polyacetic acids such as ethylenediamine tetraacetic acid and
nitrilotriacetic acid, as well as polycarboxylates such as mellitic
acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene
1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and
soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are preferred polycarboxylate builders
that can also be used in granular compositions, especially in
combination with zeolite and/or layered silicate builders.
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the
related compounds disclosed in U.S. Pat. No. 4,566,984, Bush,
issued Jan. 28, 1986.
In situations where phosphorus-based builders can be used, and
especially in the formulation of bars used for hand-laundering
operations, the various alkali metal phosphates such as the
well-known sodium tripolyphosphates, sodium pyrophosphate and
sodium orthophosphate can be used. Phosphonate builders such as
ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates
(see, for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021;
3,400,148 and 3,422,137) can also be used.
Optional Detersive Adjuncts
As a preferred embodiment, the conventional detergent ingredients
employed herein can be selected from typical detergent composition
components such as detersive surfactants and detergent builders.
Optionally, the detergent ingredients can include one or more other
detersive adjuncts or other materials for assisting or enhancing
cleaning performance, treatment of the substrate to be cleaned, or
to modify the aesthetics of the detergent composition. Usual
detersive adjuncts of detergent compositions include the
ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et
al. Adjuncts which can also be included in detergent compositions
employed in the present invention, in their conventional
art-established levels for use (generally from 0% to about 20% of
the o detergent ingredients, preferably from about 0.5% to about
10%), include enzymes, especially proteases, lipases and
cellulases, color speckles, suds boosters, suds suppressors,
antitarnish and/or anticorrosion agents, soil-suspending agents,
soil release agents, dyes, fillers, optical brighteners,
germicides, alkalinity sources, hydrotropes, antioxidants, enzyme
stabilizing agents, perfumes, solvents, solubilizing agents, clay
soil removal/anti-redeposition agents, polymeric dispersing agents,
processing aids, fabric softening components static control agents,
etc.
Bleach systems optionally, but preferably, will also comprise a
chelant which not only enhances bleach stability by scavenging
heavy metal ions which tend to decompose bleaches, but also assists
in the removal of polyphenolic stains such as tea stains, and the
like. Various chelants, including the aminophosphonates, available
as DEQUEST from Monsanto, the nitrilotriacetates, the
hydroxyethyl-ethylenediamine triacetates, and the like, are known
for such use. Preferred biodegradable, non-phosphorus chelants
include ethylenediamine disuccinate ("EDDS"; see U.S. Pat. No.
4,704,233, Hartman and Perkins), ethylenediamine-N,N'-diglutamate
(EDDG) and 2-hydroxypropylenediamine-N,N'-disuccinate (HPDDS)
compounds. Such chelants can be used in their alkali or alkaline
earth metal salts, typically at levels from about 0.1% to about 10%
of the present compositions.
Optionally, the detergent compositions employed herein can
comprise, in addition to the bleaching system of the present
invention, one or more other conventional bleaching agents,
activators, or stabilizers which are not rendered ineffective from
interaction with the nucleophilic and body soils. In general, the
formulator will ensure that the bleach compounds used are
compatible with the detergent formulation. Conventional tests, such
as tests of bleach activity on storage in the presence of the
separate or fully-formulated ingredients, can be used for this
purpose.
Specific examples of optional bleach activators for incorporation
in this invention include, hydrophobic N-acyl caprolactam bleach
activators wherein the acyl moiety contains from 6 to 12 carbon
atoms, the benzoxazin-type bleaching activators disclosed in U.S.
Pat. No. 4,966,723, Hodge et al, issued Oct. 30, 1990, and the
bleach agents and activators disclosed in U.S. Pat. No. 4,634,551,
Burns et al, issued Jan. 6, 1987. Such bleaching compounds and
agents can be optionally included in detergent compositions in
their conventional art--established levels of use, generally from
0% to about 15%, by weight of detergent composition.
Bleaching activators of the invention are especially useful in
conventional laundry detergent compositions such as those typically
found in granular detergents or laundry bars. U.S. Pat. No.
3,178,370, Okenfuss, issued Apr.13, 1965, describes laundry
detergent bars and processes for making them. Philippine Patent
13,778, Anderson, issued Sep. 23, 1980, describes synthetic
detergent laundry bars. Methods for making laundry detergent bars
by various extrusion methods are well known in the art.
The following examples are given to further illustrate the present
invention, but are not intended to be limiting thereof.
EXAMPLE I
Synthesis of Benzoyl Caprolactam--To a two liter three necked round
bottomed flask equipped with a condenser, overhead stirrer and 250
ml addition funnel is charged 68.2 g (0.6 moles) caprolactam, 70 g
(0.7 moles) triethylamine and liter of dioxane; the resulting
solution is heated to reflux (120.degree. C.). A solution of 84.4 g
(0.6 moles) benzoyl chloride dissolved in 200 ml of dioxane is then
added over 30 minutes, and the mixture is refiuxed for a further 6
hours. The reaction mixture is then cooled, filtered, and the
solvent removed by rotary evaporation to yield 121.7 g of the
product as an oil which crystallizes on standing. This crude
product is then redissolved in toluene and precipitated with
hexane, yielding 103 g (79% theoretical yield) of a white solid
which is shown by NMR to be over 95% pure, with the remaining
material being benzoic acid.
EXAMPLE II
Synthesis of Nonanoyloxybenzenesulfonate--A 500 ml 3-neck flask is
fitted with a reflux condenser and mechanical stirrer. The flask is
purged with nitrogen and charged with 0.25 moles on nonanoyl
chloride in 200 ml of dry toluene. Anhydrous p-phenolsulfonate,
monosodium salt (0.20 moles) is added as a powder, and the
resulting mixture refiuxed under nitrogen for 16 hours. The mixture
is cooled to room temperature and diluted with 200 ml diethyl
ether. The precipitated solid is collected by filtration and washed
with 100 ml of diethyl ether. The solid is triturated with 200 ml
of boiling methanol. After cooling, the solid is collected by
filtration, washed with 100 ml of methanol, and dried under vacuum.
NMR and cationic titration analyses shows the resulting
nonanoyloxybenzenesulfonate, sodium salt (0.15 moles) to be over
98% pure.
EXAMPLE III
A granular detergent composition is prepared comprising the
following ingredients.
______________________________________ Component Weight %
______________________________________ C.sub.12 linear alkyl
benzene sulfonate 22 Phosphate (as sodium tripolyphosphate) 20
Sodium carbonate 10 Sodium silicate 3 Sodium percarbonate* 20
Ethylenediamine disuccinate chelant (EDDS) 0.4 Sodium sulfate .5
Benzoyl caprolactam 5 Nonanoyloxybenzenesulfonate 5 Minors,
filler** and water Balance to 100%
______________________________________ *Average particle size of
400 to 1200 microns. **Can be selected from convenient materials
such as CaCO.sub.3, talc, clay, silicates, and the like.
Aqueous crutcher mixes of heat and alkali stable components of the
detergent compositions are prepared and spray-dried. The other
ingredients are admixed so that the detergent composition contains
the ingredients tabulated at the levels shown.
The detergent granules with bleaching system are added together
with a 6 lb. (2.7 kg) load of fabrics to a Sears KENMORE washing
machine. Actual weights of detergent and ester compositions are
taken to provide a 1000 ppm concentration of the detergent
composition in the 17 gallon (65 l) water-fill machine. The water
used has 7 grains/gallon hardness and a pH of 7 to 7.5 prior to
(about 9 to about 10.5 after) addition of the detergent
composition.
The fabrics are laundered at 35.degree. C. (95.degree. F.) for a
full cycle (12 min.) and rinsed at 21.degree. C. (70.degree.
F.).
At the end of the last rinse cycle, the test swatches are dried in
a dryer. Tristimulus meter readings (L,a,b) are then determined for
each test swatch. Whiteness performance in terms of Hunter
Whiteness Values (W) is then calculated according to the following
equation:
The higher the value for W, the better the whiteness performance.
In the above test, fabrics exposed to the bleaching system display
significantly improved whiteness after laundering compared with
fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE IV
A granular detergent composition is prepared comprising the
following ingredients.
______________________________________ Component Weight %
______________________________________ Anionic alkyl sulfate 7
Nonionic surfactant 5 Zeolite (0.1-1.0 micron) 10 Trisodium citrate
2 SKS-6 silicate builder 10 Acrylate maleate polymer 4 Benzoyl
caprolactam 10 Nonanoyloxybenzenesulfonate 10 Sodium percarbonate
25 Sodium carbonate 5 Ethylenediamine disuccinate chelant (EDDS)
0.4 Suds suppressor 2 Enzymes* 1.5 Soil release agent 0.2 Minors,
filler** and water Balance to 100%
______________________________________ *1:1:1 mixture of protease,
lipase, and cellulase. **Can be selected from convenient materials
such as CaCO.sub.3, talc, clay, silicates, and the like.
Aqueous crutcher mixes of heat and alkali stable components of the
detergent compositions are prepared and spray-dried. The other
ingredients are admixed so that the detergent composition contains
the ingredients tabulated at the levels shown.
The detergent granules with bleaching system are added together
with a 2.7 kg (6 lb.) load of fabrics to an automatic washing
machine. Actual weights of detergent and ester compositions are
taken to provide a 5000 ppm concentration of the detergent
composition in the 17 liter (4.5 gallon) water-fill machine. The
water used has 7 grains/gallon hardness and a pH of 7 to 7.5 prior
to (about 9 to about 10.5 after) addition of the detergent
composition.
The fabrics are laundered at 40.degree. C. (104.degree. F.) for a
full cycle (40 min.) and rinsed at 21.degree. C. (70.degree.
F.).
At the end of the last rinse cycle, the test swatches are dried in
a dryer. Tristimulus meter readings (L,a,b) are then determined for
each test swatch. Whiteness performance in terms of Hunter
Whiteness Values (W) is then calculated according to the following
equation:
The higher the value for W, the better the whiteness performance.
In the above test, fabrics exposed to the bleaching system display
significantly improved whiteness after laundering compared with
fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE V
A laundry bar suitable for hand-washing soiled fabrics is prepared
comprising the following ingredients.
______________________________________ Component Weight %
______________________________________ C.sub.12 linear alkyl
benzene sulfonate 30 Phosphate (as sodium tripolyphosphate) 7
Sodium carbonate 15 Sodium pyrophosphate 7 Coconut monoethanolamide
2 Zeolite A (0.1-1.0 microns) 5 Carboxymethylcellulose 0.2
Polyacrylate (m.w. 1400) 0.2 Benzoyl caprolactam 6.5
Nonanoyloxybenzenesulfonate 6.5 Sodium percarbonate 15 Brightener,
perfume 0.2 Protease 0.3 CaSO.sub.4 1 MgSO.sub.4 1 Water and
Filler* Balance to 100% ______________________________________ *Can
be selected from convenient materials such as CaCO.sub.3, talc,
clay silicates, and the like.
The detergent laundry bars are processed in conventional soap or
detergent bar making equipment as commonly used in the art. Testing
is conducted following the methods used in Example IV. In the test,
fabrics exposed to the bleaching system display significantly
improved whiteness after laundering compared with fabrics which
have not been exposed to the bleaching system of the invention.
EXAMPLE VI
A laundry bar is prepared by a procedure identical to that of
Example V, with the two exceptions that 20% of a 1:1:1 mixture of
pentanoyl caprolactam, hexanoyl caprolactam, and benzoyl
caprolactam is substituted for the benzoyl caprolactam bleach
activator, and the level of sodium percarbonate is increased to
20%. The laundering method of Example IV is repeated. In the test,
all fabrics display significantly improved whiteness after
laundering compared with fabrics which have not been exposed to the
bleaching system of the invention.
EXAMPLE VII
A laundry bar is prepared by a procedure identical to that of
Example V, with the single exception that 15% of a 1:1 mixture of
acetyl caprolactam and benzoyl caprolactam is substituted for the
benzoyl caprolactam bleach activator. The laundering method of
Example IV is repeated. In the test, all fabrics display
significantly improved whiteness after laundering compared with
fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE VIII
A laundry bar is prepared by a procedure identical to that of
Example V, with the single exception that an equivalent amount of
3,5,5-trimethylhexanoyloxybenzenesulfonate is substituted for the
nonanoyloxybenzenesulfonate bleach activator. The laundering method
of Example IV is repeated. In the test, all fabrics display
significantly improved whiteness after laundering compared with
fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE IX
A laundry bar is prepared by a procedure identical to that of
Example V, with the exceptions that 6% of a 1:1 mixture of benzoyl
caprolactam and a benzoxazin-type bleach activator, as disclosed in
U.S. Pat. No. 4,966,723, is substituted for the benzoyl caprolactam
bleach activator and an equivalent amount of
2-ethylhexanoyloxybenzenesulfonate is substituted for the
nonanoyloxybenzene sulfonate bleach activator. The laundering
method of Example IV is repeated. In the test, all fabrics display
significantly improved whiteness after laundering compared with
fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE X
A bleaching system is prepared comprising the following
ingredients.
______________________________________ Component Weight %
______________________________________ Benzoyl caprolactam 15
Nonanoyloxybenzenesulfonate 15 Sodium percarbonate 45 Chelant
(ethylenediamine disuccinate, EDDS) 10 Filler* and water Balance to
100% ______________________________________ *Can be selected from
convenient materials such as CaCO.sub.3, talc, clay silicates, and
the like.
Testing is conducted following the methods used in Example V with
the single exception that the an equivalent amount of the above
bleaching system is substituted for the detergent composition used
in Example V. In the test, fabrics exposed to the bleaching system
display significantly improved whiteness after laundering compared
with fabrics which have not been exposed to the bleaching system of
the invention.
While the compositions and processes of the present invention are
especially useful in conventional fabric laundering operations, it
is to be understood that they are also useful in cleaning system
which involves low water:fabric ratios. One such system is
disclosed in U.S. Pat. No. 4,489,455, Spendel, issued Dec. 25,
1984, which involves a washing machine apparatus which contacts
fabrics with wash water containing detersive ingredients using a
low water: fabric ratio rather than the conventional method of
immersing fabrics in an aqueous bath. The compositions herein
provide excellent bleaching performance in such mechanical systems.
Typically, the ratio of water:fabric ranges from about 0.5:1 to
about 6:1 (liters of water:kg of fabric).
EXAMPLE XI
Using the machine and operating conditions disclosed in U.S. Pat.
No. 4,489,455, cited above, 25 grams of a composition according to
Example V herein are used to launder fabrics with concurrent
bleaching. If desired, sudsing of the composition can be minimized
by incorporating therein from 0.2% to 2% by weight of a fatty acid,
secondary alcohol, or silicone suds controlling ingredient. In the
test, fabrics exposed to the bleaching system display significantly
improved whiteness after laundering compared with fabrics which
have not been exposed to the bleaching system of the invention.
Contrary to the teachings of U.S. Pat. No. 4,545,784, cited above,
the bleach activator is preferably not absorbed onto the peroxygen
bleaching compound. To do so in the presence of other organic
detersive ingredients could cause safety problems. It has now been
discovered that the caprolactam bleach activators of this invention
can be dry-mixed with peroxygen bleaching compounds, especially
perborate, and thereby avoid potential safety problems.
EXAMPLE XII
A laundry bar suitable for hand-washing soiled fabrics is prepared
comprising the following ingredients.
______________________________________ Component Weight %
______________________________________ Linear alkyl benzene
sulfonate 30 Phosphate (as sodium tripolyphosphate) 7 Sodium
carbonate 20 Sodium pyrophosphate 7 Coconut monoethanolamide 2
Zeolite A (0.1-1.0 microns) 5 Carboxymethylcellulose 0.2
Polyacrylate (m.w. 1400) 0.2 Benzoyl caprolactam 5
Nonanoyloxybenzenesulfonate 5 Sodium perborate tetrahydrate 10
Brightener, perfume 0.2 Protease 0.3 CaSO.sub.4 1 MgSO.sub.4 1
Water 4 Filler* Balance to 100%
______________________________________ *Can be selected from
convenient materials such as CaCO.sub.3, talc, clay silicates, and
the like.
The detergent laundry bars are processed in conventional soap or
detergent bar making equipment as commonly used in the an with the
bleaching activator dry-mixed with the perborate bleaching compound
and not affixed to the surface of the perborate. Testing is
conducted following the methods used in Example IV. In the test,
fabrics exposed to the bleaching system display significantly
improved whiteness after laundering compared with fabrics which
have not been exposed to the bleaching system of the invention.
EXAMPLE XIII
A laundry bar is prepared by a procedure identical to that of
Example XII, with the single exception that an equivalent amount of
2-ethyloxybenzenesulfonate is substituted for the nonanoyloxy
benzenesulfonate bleach activator. The laundering method of Example
IV is repeated. In the test, all fabrics display significantly
improved whiteness after laundering compared with fabrics which
have not been exposed to the bleaching system of the invention.
EXAMPLE XIV
A laundry bar is prepared by a procedure identical to that of
Example XII, with the exceptions that 6% of a 1:1 mixture of
benzoyl caprolactam and hexanoyl caprolactam is substituted for the
benzoyl caprolactam bleach activator and 6% of a 1:1 mixture of
dodecanoyloxybenzenesulfonate and decanoyloxybenzenesulfonate is
substituted for the nonanoyloxybenzenesulfonate bleach activator.
The laundering method of Example IV is repeated. In the test, all
fabrics display significantly improved whiteness after laundering
compared with fabrics which have not been exposed to the bleaching
system of the invention.
EXAMPLE XV
A laundry bar is prepared by a procedure identical to that of
Example XII, with the single exception that 10% of a 1:1 mixture of
benzoyl caprolactam and a benzoxazin-type bleach activator, as
disclosed in U.S. Pat. No. 4,966,723, is substituted for the
benzoyl caprolactam bleach activator. The laundering method of
Example IV is repeated. In the test, all fabrics display
significantly improved whiteness after laundering compared with
fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE XVI
A laundry bar is prepared by a procedure identical to that of
Example XII, with the single exception that 6% of a 1:1 mixture of
benzoyl caprolactam and a bleach activator, as disclosed in U.S.
Pat. No. 4,634,551, cited above, is substituted for the benzoyl
caprolactam bleach activator. The laundering method of Example IV
is repeated. In the test, all fabrics display significantly
improved whiteness after laundering compared with fabrics which
have not been exposed to the bleaching system of the invention.
EXAMPLE XVII
A granular detergent composition is prepared comprising the
following ingredients.
______________________________________ Component Weight %
______________________________________ Linear alkyl benzene
sulfonate 20 Phosphate (as sodium tripolyphosphate) 20 Sodium
carbonate 10 Sodium silicate 3 Sodium perborate tetrahydrate 20
Ethylenediamine disuccinate chelant (EDDS) 0.4 Sodium sulfate 5.5
Hexanoyl caprolactam 5 Nonanoyloxybenzenesulfonate 5 Minors,
filler** and water Balance to 100%
______________________________________ **Can be selected from
convenient materials such as CaCO.sub.3, talc, clay, silicates, and
the like.
Aqueous crutcher mixes of heat and alkali stable components of the
detergent compositions are prepared and spray-dried. The other
ingredients are dry-mixed so that the detergent composition
contains the ingredients tabulated at the levels shown.
Testing is conducted following the methods used in Example IV. In
the test, fabrics exposed to the bleaching system display
significantly improved whiteness after laundering compared with
fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE XVIII
A granular detergent composition is prepared by a procedure
identical to that of Example XVII, with the single exception that
15% of a 1:1 mixture of benzoyl caprolactam and hexanoyl
caprolactam is substituted for the hexanoyl caprolactam bleach
activator. The laundering method of Example IV is repeated. In the
test, all fabrics display significantly improved whiteness after
laundering compared with fabrics which have not been exposed to the
bleaching system of the invention.
EXAMPLE XIX
A granular detergent composition is prepared by a procedure
identical to that of Example XVIII, with the single exception that
6% of a 1:1 mixture of benzoyl caprolactam and a benzoxazin-type
bleach activator, as disclosed in U.S. Pat. No. 4,966,723, is
substituted for the hexanoyl caprolactam bleach activator. The
laundering method of Example IV is repeated. In the test, all
fabrics display significantly improved whiteness after laundering
compared with fabrics which have not been exposed to the bleaching
system of the invention.
EXAMPLE XX
A granular detergent composition is prepared by a procedure
identical to that of Example XVIII, with the single exception that
6% of a 1:1:1 mixture of octanoyloxybenxenesulfonate,
decanoyloxybenzenesulfonate and a benzoxazin-type bleach activator,
as disclosed in U.S. Pat. No. 4,634,551, cited above, is
substituted for the nonanoyloxybenezenesulfonate bleach activator.
The laundering method of Example IV is repeated. In the test, all
fabrics display significantly improved whiteness after laundering
compared with fabrics which have not been exposed to the bleaching
system of the invention.
A particularly preferred embodiment of this invention is a
1:2.2:7.7 molar ratio of N-acyl caprolactam to
alkanoyloxybenzenesulfonate to peroxygen bleaching compound. This
mixed caprolactam alkanoyloxybenzenesulfonate bleaching composition
delivers stronger than expected performance on hydrophobic stains
and hydrophilic stains and on dingy clean up.
EXAMPLE XXI
A laundry bar is prepared by a procedure identical to that of
Example V, with the exceptions that the level of benzoyl
caprolactam is 0.85%, the level of nonanoyloxybenzenesulfonate
bleach activator is 3% and sodium percarbonate is substituted with
3% perborate. The laundering method of Example IV is repeated. In
the test, all fabrics display significantly improved whiteness
after laundering compared with fabrics which have not been exposed
to the bleaching system of the invention.
EXAMPLE XXII
A granular laundry detergent is prepared by a procedure identical
to that of Example III, with the exceptions that the level of
benzoyl caprolactam is 0.85%, the level of
nonanoyloxybenzenesulfonate bleach activator is 3% and sodium
percarbonate is substituted with 3% perborate. The laundering
method of Example III is repeated. In the test, all fabrics display
significantly improved whiteness after laundering compared with
fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE XXIII
A granular laundry detergent is prepared by a procedure identical
to that of Example IV, with the exceptions that the level of
benzoyl caprolactam is 0.85%, the level of
nonanoyloxybenzenesulfonate bleach activator is 3% and sodium
percarbonate is substituted with 3% perborate. The laundering
method of Example IV is repeated. In the test, all fabrics display
significantly improved whiteness after laundering compared with
fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE XXIV
A laundry bar is prepared by a procedure identical to that of
Example XI, with the exceptions that the level of benzoyl
caprolactam is 0.85%, the level of nonanoyloxybenzenesulfonate
bleach activator is 3% and the level of sodium perborate
tetrahydrate is 3%. The laundering method of Example XI is
repeated. In the test, all fabrics display significantly improved
whiteness after laundering compared with fabrics which have not
been exposed to the bleaching system of the invention.
EXAMPLE XXV
A granular laundry detergent is prepared by a procedure identical
to that of Example XVII, with the exceptions that the level of
nonanoyloxybenzenesulfonate bleach activator is 3%, the level of
sodium perborate tetrahydrate is 3%, and the hexanoyl caprolactam
is substituted with 0.85% benzoyl caprolactam. The laundering
method of Example XVII is repeated. In the test, all fabrics
display significantly improved whiteness after laundering compared
with fabrics which have not been exposed to the bleaching system of
the invention.
While the foregoing examples illustrate the use of the present
technology in cleaning/bleaching compositions designed for use in
laundering, it will be appreciated by those skilled in the art that
the bleaching systems herein can be employed under any circumstance
where improved oxygen bleaching is desired. Thus, the technology of
this invention may be used, for example, to remove stains and
cleans dishes, to bleach paper pulp, to bleach hair, to cleanse and
sanitize prosthetic devices such as dentures, in dentifrice
compositions to clean teeth and kill oral bacteria, and in any
other circumstances where bleaching is advantageous to the
user.
EXAMPLE XXVI
A granular automatic dishwashing detergent composition wherein
stain removal and cleaning benefits are achieved is prepared
comprising the following ingredients.
______________________________________ % by weight of active
material Component A B C ______________________________________
Citrate 15.00 15.00 20.00 Acusol 480N.sup.1 6.00 6.00 6.90 Sodium
carbonate 20.00 20.00 23.00 Britesil H.sub.2 O) (SiO.sub.2) 9.00
9.00 7.50 Nonionic surfactant.sup.2 2.00 2.00 2.00 Savinase 12T
2.00 2.00 2.00 Termamyl 60T 1.00 1.00 1.00 Percarbonate (as AvO)
1.50 1.50 1.50 Nonanoyloxybenzenesulfonate 2.00 2.00 2.00
Benzoylcaprolactam 2.00 3.80 2.00 Diethylene triamine pentaacetic
acid 0.13 0.13 0.13 1,1-hydroxyethanedishosphonic acid 0.50 0.50
0.50 Sulfate, water, etc. Balance to 100% pH 10.0 10.0 10.0
______________________________________ .sup.1 Dispersant from Rohm
and Haas .sup.2 Low cloud, high HLB nonionic surfactant
EXAMPLE XXVII
Tablet compositions of the present invention are as follows:
______________________________________ Component % by weight of
active material ______________________________________ Citrate
20.90 20.90 Phosphate -- -- Polyacrylate 2.70 2.70 Carbonate 14.00
14.00 1,1-hydroxyethanedishosphonic 0.36 0.36 acid Silicate
2r(SiO2) 12.20 12.20 metaSilicate (SiO2) -- -- Paraffin 0.36 0.36
Benzotriazole 0.21 0.21 Perborate tetrahydrate (as AvO) 0.64 0.64
Perborate monohydrate (as AvO) 0.22 0.22 Percarbonate (as AvO) --
-- Nonanoyloxybenzenesulfonate 2.00 2.00 Benzoylcaprolactam 3.20
5.10 Phenylbenzoate -- -- Diethylene triamine pentamethy- 0.09 0.09
lene phosphoric acid Savinase 60T 1.10 1.10 Savinase 12T 1.58 1.58
Nonionic surfactant 1.18 1.18 Termamyl 60T 1.10 1.10 Sulfate,
water, etc. Balance to 100% pH 11 11
______________________________________
Automatic dishwashing compositions may be in granular, tablet, bar,
or rinse aid form. Methods of making granules, tablets, bars, or
rinse aids are known in the art. See, for instance, U.S. patent
Ser. Nos. 08/106,022, 08/147,222, 08/147,224, 08/147,219,
08/052,860, 07/867,941.
* * * * *